Superfatted soap bar containing a synergistic preservative mixture of ehdp and edta



y 2, 1970 J. w. WARM 3,511,783

SUPERFATTED SOAP BAR CONTAINING A SYNERGISTIG PRESERVATIVE MIXTURE OF EHDP AND EDTA Filed March 7, 1967 E91. 52 I 25 i AI 2555 27- 2555' I Z6. 2569 2575 Z 2555 g 2559 2555 2575 I l 2; P 25555577 I /5- 2542 77 2575' /5- 255/ Z; 2572 2552 2 2557 I 2575 I 2555 75- 255/ 2571 In venfor Jo/m Wa/fer Waging B M fame a Sheets-Sheet 1' May 12, 1910 J. w. WARING 3,511,783 SUPERFATTED SOAP BAR CONTAINING A SYNERGISTIC PRESERVATIVE MIXTURE OF EHDP AND EDTA 3 Sheets-Sheet 2 Filed March 7, 1967 Q 2567 I I Inventor v John Waller Waring 7 Home * May 12, 1970 Filed March 7, 1967 J. w. WARING 3,511,783 SUPERFATTED SOAP BAR CONTAINING A SYNERGISTIC PRESERVATIVE MIXTURE OF EHDP AND EDTA 3 Sheets-Sheet 5 50f F4 a. 25-

22 M 25 /.7- I if 2572 I 252/ I 4 2575 2557 2 /2 257/ 2550 I m- 2552 9- 255/ 2525 2555 2554 255/ I 255/ I 2555 2552 )I 2552 0 In venfor John a/fe War/n United States Patent 3,511,783 v SUPERFATTED SOAP BAR CONTAINING A SYNERGISTIC PRESERVATIVE MIXTURE 0F EHDP AND EDTA John Walter Waring, Wirral, England, assignor to Lever Brothers Company, New York, N.Y., a corporation of Maine Filed Mar. 7, 1967, Ser. No. 621,248 Int. Cl. Clld 9/48, 9/34, 9/30 US. Cl. 252-117 1 Claim ABSTRACT OF THE DISCLOSURE A detergent bar is preserved against deterioration of odour and colour by incorporation of a synergistic mixtureof EHDP and EDTA.

This invention relates to detergent bars.

Common faults in a finished bar are that the bar develops spotting or overall discoloration and that the base odour of the detergent deteriorates.

It is generally accepted that the most probable cause of rancidity,.r'leterioration of base odour, in detergent bars, is oxidation of long-chain unsaturated and saturated compounds. The development of spotting or overall discoloration is less clearly understood. It often accompanies deterioration of base odour.

-The presence of heavy metals or their salts is known to beflanimportant cause of deterioration of base odour, spotting and discoloration of detergent bars. This cause could be eliminated by ensuring that the ingredients of the bar are free from such metals and that the detergent during its manufacture and processing does not come into contact with them. Since as little as 0.2 part per million copper, in the absence of preservatives, has been shown to have a significant elfect on colour and odour deterioration, this solution would be very expensive and so is not satisfactory commercially.

" alternative solution is to use a sequestering agent. The mechanism for the oxidation of long-chain fatty compounds is generally believed to be by a free radical chain reaction. The free radicals required to propagate a chain reaction may be initiated either by traces of heavy metals, or photochemically or thermally. In normal detergent bars, without preservatives, trace metal contamination is responsible for a far higher rate of development of colour and odour than normal amounts of heat and light. Sequestering agents operate by lowering the concentration of heavy metal ions in the bar, and hence lower the rate of free radical initiation.

, Other antioxidants frequently used act by absorbing free radicals and thus terminate chain reactions independently of the method of initiation. in this process, the antioxidant is itself destroyed. Thus it is desirable to include a sequestering agent to lower the rate of initiation of free radicals. Inaddition to the sequestering agent another antioxidant is often included to absorb free radicals'initiated by any residual metal ions, or by photochemical or thermal energy sources.

A particular problem is the prevention of deterioration of'base odour, spotting and discoloration in super-fatted detergent bars, for example, in soap bars containing significant amounts of free fatty acid.

A typical super-fatted soap contains 10% (calculated -as a percentage of the total fatty matter) of free fatty acids but soaps containing 20% of free fatty acid are known. The presence of metal ions, particularly iron and copper ions, in these soaps can be particularly troublesome: Petrolatum, mineral oils, lanoline or other such super-fatting agents can be used as well as fatty acids added separately or specially released in the bar.

Patented May 12, 1970 A super-fatted non-soap detergent bar can contain as glycols, fatty acid amides, long-chain alkanolamides, in

particular isopropanolamides, and esters.

It has now been discovered that by incorporating a long-chain acid sugar mixture of sequestering agents, ethane-l-hydroxy-l, l-

diphosphonic acid, hereafter called EHDP, l,2-diaminoethane-N,N-N,N-tetraacetic acid, commonly called ethylene-diaminetetraacetic acid and hereafter called EDTA, in a detergent bar, a bar is obtained which is especially resistant to the development of rancidity, spotting or overall discoloration. 4

It is understood that the EHDP, the EDTA or bo may be in the form of their esters or, preferably, in the form of their salts. Particularly preferred salts are the alkali-metal, ammonium or triethanolammonium,salts.

It has been discovered that a detergent bar that is particularly resistant to the development of rancidity, spotting or overall discoloration can be obtained using a smaller quantity of a mixture of EHDP and EDTA than would be expected from a knowledge of the affect of these compounds separately.

The invention provides a detergent bar containing a' synergistic mixture of EHDP and EDTA.

The actual quantity of EHDP and EDTA used will depend to some extent on the particular detergent used but bars according to the invention can be provided by incorporating as little as 0.005% of EHDP in admixture with as little as 0.005% of EDTA. The quantity of EHDP will, in general, be from 0.005% to 0.3% or even higher and that of EDTA 0.005 to 0.3% or higher.

A preferred detergent bar according to the invention contains between 0.01% and 0.08% EHDP and 0.01% and 0.08% EDTA by weight.

A particularly preferred detergent bar according to the invention contains about 0.02% EHDP and about 0.02% EDTA by weight.

The invention is particularly applicable to toilet bars for personal washing.

The invention is even more particularly applicable to super-fatted toilet bars for personal washing. In such bars deterioration in odour and colour is least welcome and the effect of metal ions is most acute as explained above. Although the invention is particularly applicable to a detergent bar in which the detergent is soap, it will be appreciated that the invention is applicable to any detergent bar that contains an ingredient that contains a long-chain fatty residue. Such ingredients are liableto cause the odour and colour of the bar to deteriorate when metal ions, particularly copper and iron, are also present.

By an ingredient that contains a long-chain fatty residue is meant a compound containing a C to C preferably C to C group. The chain may be branched but should preferably be straight. The compound will normally contain functional groups, as illustrated below. The C to C group may contain one or more double bonds.

The invention is, for example, applicable to detergent bars containing, as major active, such non-soap detergents as olefin sulphonates (prepared by the sulphonation of olefins followed by hydrolysis and neutralisation), fatty acyl isothionates, fatty acyl taurides and fatty alcohol sulphates.

It will be appreciated that the invention is also applicable to bars containing mixtures of soap and non-soap detergents. In particular the invention is applicable to bars containing a major proportion of a non-soap detergent together with a minor proportion of soap.

I EXAMPLE I- Lxamples of non-superfatted toilet bars according to invention were prepared and compared with bars coning EHDP and EDTA separately and with bars coning neither EHDP nor EDTA as follows:

Method of manufacture: Non-superfatted bars large batch of dried soap chips, manufacture from 30% Tallow/20% Palm Kernel Oil fat charge, was 'oughly mixed to ensure homogeneity. Special precaus were taken to minimise metallic contamination in chips. The batch was sub-divided into 16 sub-batches to each of 15 of these .was added fixed quantities of lution of EDTA and/or a solution of EHDP. In this 16 batches were obtained with all possible combinas of any one of 4 levels of EDTA (0, 0.03, 0.12 or with any one of 4 levels of EHDP (0, 0.03, 0.12 0.48%).

ach of the sub-batches was thoroughly mixed and ed through a three-roll soap mill three times to ensure orm, distribution of the metal deactivators EDTA EHDP.

sch sub-batch was then again divided into 3 equal s. To one part was added 1 p.p.m. copper, in the form I. dilute solution of copper sulphate, and 1t) p.p.m. in the form of a dilute solution of ferrous ammonium hate. Similarly, to the second part 2 p.p.m. copper and p.p.m. iron were added; no additions were made to third portion. Each of the 48 sub-batches thus pro- :d was thoroughly mixed, milled three times in conional three-roll soap mills, and extruded through a rentional vacuum refiner plodder.

he final moisture content of the bars was similar to of conventional toilet soap at 11-12% (total fatty ter 78-79%). Apart from the materials specified ve no other ingredients were included; thus the tablets ained no other preservatives or ingredients which are uently-included in toilet soaps, such as perfume, rescer, opacifier etc. 7

he ratio of copper/iron chosen approximates to the age ratio found in practice. Up to 1 p.p.m. copper 10 p.p.m. iron are frequently found in practice.

Methods of, storage Method of assessment dour was assessed by panels of assistants, experienced ssessing odour in this way, but not especially trained. assessment was planned on a statistical basis to enthe significance of the data to be determined. The 48 :hes stored under one set of conditions were compared 1 one another and the procedure repeated for the other sets or conditions. A design wasused in which each was compared in turn with each, of the other 47 bars. Thus 1128 pairs were compared, each pair twice (once for each order of testing), and each single soap was assessed 94 times. The panel consisted of 113 girls: to avoid fatigue of the olfactory organs, each assistant compared only one pair at a time and not more than 4 pairs during the course of an 8 hour working day. In the comparisons, the panel members were asked to smell the bars with closed eyes (thus to prevent any influence of colour differences) and to express an opinion on which bar has the stronger odour. Since the samples were unperfumed, this is a direct measure of the strength of the undesirable base odour.

Each answer was scored +1 for the tablet with the strongest odour, 0 for no difference and 1 for that with the weakest odour. The scores for each panel member for each bar were added together to arrive at the total score for each bar. A low score indicates little base odour (good preservation) and a high score indicates strong base odour (poor preservation).

The scores for each Of the three sets of storage conditions were added together to give the results given in Table I.

TABLE I- Before addition or further copper and iron:

Base level of copper, 0.3 p.p.m. Base level of iron, 4.6 p.p.m.

Percent EDTA (N o 00 or inanddrid): pp

Percent EHDP Percent EDTA (1 ppm.

cogggr/IO p.p.m. ron added):

Percent EHDP 0 Percent EDTA (2 .m'.

his added):

ea or 0 .m. 828.522--- Percent EHDP 0 Standard error of dillerenec 24.1. There is a 19/1 probability of a true diiference.

dillerence of 48.2 being :1.

EXAMPLE II In the following series of bars, covering the use of difierent levels of copper and iron contamination, a different design pattern was used from that in Example I and the method of manufacture and testing were slightly changed.

Method of manufacture: Non-superfatted bars A large batch of dried soap chips, manufactured from an tallow/20% palm kerneloil fat charge was thoroughly mixed to ensure homogeneity. Special precautions were taken to minimise metallic contamination in the chips. The batch was sub-divided into 30 sub-batches;

'51 Methods of storage ':.'As described *in E- xarnple It -;Method;ofassessrnent TABLE IV Efiectoi EHDP and EDTA on Non-superfat te'd Toilet Bars containing ggpper and Iron Contaminants-Total Scores irom Panel Test for our Storage conditions;

dour The methodiis Semi as qescfibed in 28 days egrposed to the atmosphere. unwrapped, at 37 OJ relaample 1, but the numbers of tests were different to allow five m y. in e a c yi lummation; I I

Before addition of further copper and iron:

Base level of copper, 0.3 p.p.m.

Base level of iron, 6.5 p.p.m.

forthe smaller number gf batchesx Jneachrtestt'aidesignwasmsed nawhicheach of the v30 batches was compared in turn with each of the other 29 b h Th 435 d h No Copper/Iron Added atc es. us pairs ;,were compare eac pair twice :(once for each order of testing) and each single'soap was P F Ff S fffffig g assessed 58 times. Thevvpanelconsisted of 40-45 girls. g

{Restrictions to-av'oid olfactory fatigue, questions asked andscoringrnethodswqe the same as described in Example 1. In the following tables for individual storage con- 5 EHDP 0 5 difions 'a difie'rence Between the scores of 22 is significant 0.5 p.p.m. Copper/5 p.p.m. Iron Added at-the 95% probability level: i.e. there is a 19/1 prob- I Percent EDTA (as free acid)- ability of a difference of 22-be1ng a true difference. Sigmfi- 0 9eas udat iqwrtab e ,rear ss tm the Sum of Scores from +3 -5 -17 all storage conditions are given with the tables. 5 +9 -16 1 TABLE II Percent EHDP 0 0.02 0.1 0.5

Eflec't a: EHDR and EDTA on Non-superfatted Toilet Bars containing 1 .00 e 10 .IronAdded Copper and Ir gontaminantg-Total Scores from Panel Test for w 0111' Storage conditions: 28 days exposed unwrapped in awindow to northern day ght. t +14 7 Bero r e Additign of furthes gopper and iron: ase eve 0 copper .m; 2 4

B sr loiltw h m-1;? +31 5 5 E 0. 02 0. 1 0. 5 y y w a I Percent ED]? 0- TABLE v Effect of EHDP and EDTA on Non-superfatted Toilet Bars containing Copper and Iron Contaminants'Summation 0! Scores from Panel Tests for Odour irom three sets of Storage Conditions Base level eopper, 0.3 p.p.m. '1 02 1 5 Base level iron, 6.5 p.p.m.

r. s 0.6'p".p.m-.' qopperlfi p.p.n'i. Iron added No-copperlImn Added Percaegt EDTA (as free may 9 011 -s 7 -a1 I r i. 9 7

0.5 ppm. Copper/5 p.p.m. Iron Added Percent EHDP 0 0.02 1 ,5 0 0.02 0.1 0.5

i 1 ..m.oo 10 ..m.IronAdded TABLE PP pp r/ p 7 ,Efleet 0mm)? and-.EDTA 6 Non sfiperiatted Toilet Bars containing 5 EDTA (as free add): +19

ggppor and Iron Contaminants T0tol Scores from Panel Test for 0 our Storage conditions: 28 days exposed to the atmos here unwra ed at a 031%? g ii emeiofaln-y-illuminant;111; p pp +74 4 e ore e a on 0 ur or copper an on: 0 Base levelotcopperq ofip'p'mh 7 Percent EHDP 0 0.02 0. 1 0. 5

Base level of iron, 6.5 p.p.m. Y v

- Standard error of difference 19, a ditference of '38 is signifi- N0 copp /i n added cunt at the 95% probability level.

Percent EDTA. (as free acid) v .5 13

ExaMPLE HI Method-of manufacture: Superfattedsoap A large batch of soap] was manufactured from a 5 0% tal1ow/50% palmkernel oil fat charge and -sup'erfatted 2 .114 byt e ti of .10 fattya (calculated b centage of total'tattey matter), prepared-by acidification of the same soap base. Special precautions were taken to minimise metallic contamination in the final dried superfatted soap'chipsi Preparation of the 30sub-batches undertaken in +19 exactly the same manner 'as that of the non-superfatted +28 +30 0 -14 i59 155 tEii F P fill' j lama; EHpiflWw-ffm The storage methods were those used 1n Example 11.

15 Odour wasassessed-as-describediii-Example In,

Jolour was assessed as follows:

iwenty-five girls were asked to rank the bars in each rage experimentinorder of whiteness. Score 1 for the itest, 2 for the next whitest and so on. The mean result each bar-is given in the tables.

5 Before addition of any further copper or iron: [he odour and colour results obtained are set out in 3:: m3 g per. g-g p-p-m. ales VI 'to XII.

No Copper/Iron Added lere er it EDTA (as tree acid): 1 0Z1: 0 -1o 3- 2, 1%; 2 TABLE'VI at of nnnr and EDTA on Bu atted Toilet Bars containing 5 zipper and Iron Contaminanteotal Scores from Panel Test for ppm' corset/5 palm nun our: egg eo gd igions: 28 days exposed unwrapped in a window to north- I A 1- I we addition of further copper and iron: "3? EDTA (as free acid) +6 Base level of copper, 0.6 p.p.m. +17 8 Base-level oi iron, 8.9 p.p.m. +10 9 -12 I No Copper/Iron Added "f +14 but EDTA (as free acid): Percent EHDP 0 0.02 0.1 0.5 ii

2 2 -2 1 p.p.m. flopgsrfigpmm. Iron +5 0 -17 --23 Percent EHDP-.. o 0.02 0.1 0.5 25 ff? "16)? +24 -4 I 0.5 p.p.m. Cop l5 p.p.m. Iron Am +19 +12 -9 +10 fg (as fi +23 Percent nnnr-....----- o o. 02 0.1 o. 5 +8 -1:

Percent EHDP.-. 0 I 0.02 0. 1 0. 8 TABLE. Ix

1 D-P 123 7 P-P- mm Eilect oiEHDP and ED'IA on Superiatted Toilet Bars containing Cop;

perggd Iron cgx temln ant sfiummgtiog ol Scores from Panel ,Tea I 011! out ED'IA (as free acid): +15 Ba s level c0533, 023. 351? rage on 0118 ii; 3 7 Base level iron, 8.9 p.p.m. +10 +13 +14 No Copper/Iron Added Percent nnnr o 0. 2 0.1 o. 5 4o %?fiff +29 0.1.. +25 -34 0.02... 53 52 -34 0-........-.....-.-.. +24 -s -ee 52 Percent KHDP.....-..... 0 0.02 0.1 0.5

0.5 .p.m. Cop [6 p. .m. Iron p Afi d p TABLE v11 4 Perc egt ED'IA. (as iree acid)- it oi EHDP and EDTA on Bu atted Toilet Bars containing +64 41 I ipper" and Iron contaminants-Tm Scores from Panel Test ior igg :33 u our:

conditions: 8 do exposed the atmoe here, unwrapped r any. relative hu n iidity m thmbsenee oi an y illumination. Percent EHDP- 0 02 -1 5 re addition oi any iurther copper and iron: Bale 1673 of opper oj p.p.m. M 1 p.p.m. Cor u-J10 p.p.m. Iron No Copp /Iron Added d ed t EDTA as free acid +14 +51 10 +27 --22 +gg a -5 --9 01 +19 -8 12 6 +26 -42 +8 o 0, 0g 0 1 o, 5 Percent EHDP 0 0. 0B 0. 1 0. 5

I 60 0.5 p.p.m. Copam' 5 p.p.m. Iron A ded TABLE X Efiect oi EHDP and EDTA on Buperfatted Toilet Bare containing +15 Copper andliron Contamlnation-Total 8cores (ranking method) from +29 20 Panel Test for Colour 2; -21 i3 2 5 Biggage conditions: 28 days exposed unwrapped in a window to northern Beto e addition of iurther copper and iron:

Percent EHDP..... 0 0. 02 0. 1. 0. 5 Base level of copper, 0.6 p.p.m.

1 p.p.m. 001233183 p.p.m. Iron TABLE VIII Efieet oi EHDP and EDTA on Superiatted Toilet Bars containing Cop er and Iron Contaminants-Total Scores from Panel Test for Odour tgrage conditions: 28 days exposed to the atmosphere, unwrapped at 46 C. in the absence of any illumination.

Base level of iron, 8.9 p.p.m.

p N o Copper/Iron Added mt nn'm (as free acid): Percent EDTA (as free acid): L6 +22 27. 3

Percent EHDP-....---.. 0.. 0.02 0.1 0.5 Percent EHDP.... 0 0.02 0.1 0.5

TABLE X Coutim1e 1 Table XIII gives the significance dataon odour scores;

0.5 .m. per/6 p.p.m. Iron TABLE XIII p p Zdded Difference Percent EDTA (as free acid) between scores 0.5 29. 4 tor significance 0. 25. 1 13. O 5 Standard at the 95% 0. '20. 8 6. 5 2. 7 error of probability 0- 24. 0 11. 8 17.0 14. 6 difierence level 0 0. 02 0- 1 5 28 days exposure to deylig ht 11. 0 2 1 0 I10 11 555 ii 8"2'57"1i'i1" ii'% 55 .m. 0 per '1). .m. on a s e p p ?Added. p 10 Sum ztscoresnluj 19. 0 38 The significance levels at 95% confidence limits for the colour data are given in FIGS. 1, 2 and 3. These were ca1- culated from the ranking results by statistical analysis. Percent EHD]? 0 0. 02 0.1 0.5 15

TABLE XI Effect of EHDP and EDTA on Superlatted Toilet Bars containing Cop er and Iron Contaminants-Total Scores (ranking method) from TABLE XIV anel Test for Colour Storage wnditions! 28 y exposed to the atmosphere, unwrapped at [Key to batch reference numbers for use with FIGS. 1, 2end 3 for colour] 45 C. in the absen ce of any illumination. Before the addition of further copper and iron: No Copper/Iron Added Base level of copper, 0.5 p.p.m. Base level of iron, 8.9 p.p.m. P0113315 EDTA (as free acid): 55

No Copper/Iron Added 011 2556 2557 2 6 Percent EHDP- 0 0.02 0.1 0.5 0.5 .m. Cop er/5 p.p.m. Iron p D Added Percent EHDP 0 0 02 0. 1 0. 5

------ Percent EDTA (as free acid):

0.5 p.p.m. Copper/5 p.p.m. Iron 0,5 2563 Added 2566 2567 2563 2564 2565 Percergt EDTA (as free acid): 26 2 2559 2560 2561 2562 2610 12. 8 Percent EHDP o 0.02 o. 1 0. 5

21.0 7.9 7.4 28. 8 16. 4 15. 4 10. 8 I Ir 1 .m. 00 er 10 .m. on 0 0. 02 0. 1 0. 5 p p Adde d 1 .m. 00 p r/ Perce tEDTA f 0 acid pp Added 0.; 3 11? 7s Percent EHDP 0 0. 02 0. 1 0. 5

TABLE XII Efiect of EHDP and EDTA on So erfatted Toilet Bars Containiu Copper and Iron (lontaminatiouz Total Scores (ranking method 1 15 for 28 days exposure to northern dayhght St ri' i 28 (1 10m d t th t h a t (Table Y orage 00D. 1 1011s: ays expose 0 9 a mos ere unwra e a 37 C./25% relative humidity, intheabsence of a ilyilliiminati 2 for 28 y at (Table Befigggigggirzgiggigercgogrieihlend iron: FIG. 3 is for 28 days at 37 C. and 25% relative Base level of iron, 8.'9 p.p.in: i i iyG (T N0 C(mper/Imn Added 0-4.5=very light cream 2 4.5-19.2=1ight cream 9 g 19.2-21.35=cream g 5-2 '-g 3 2 21.35-25.5=dark cream 2.5.5-3 0=vcry dark cream 0 0.02 0.1 0. 5 In FIG 0.5 p.p.m. Copper/5 p.p.m. Iron Added 14-20.3=dark cream Percent EDTA (as free acid): 20.3-23.4=1ight brown l4 3 23.427.1=brown 20.0 1011 10. 4 05 27 .1-30.0 =dark brown 20.7 12.4 10.7 12.1 In FIG Percent EHDP 0 0. 02 0. 1 o. 5 0-1 1.7 =cream 11 7-21 4==dark cream 1 p. .m. 00 er/lO .111. Iron p filmed p p 21.4-24.4=11ght brown 24.430.0= br0Wn What is claimed is: 1. A superfatted soap bar stabilized against deteriora' tion of odor and color caused by copper and iron con- Pemnt EHDP 0 0 02 M tammants by a synerg1st1c preservative mixture of aboui 0.02% of ethane-l-hydroxy-l, l-diphosphonic acid and mt 0.02% of ethylenediamine tetraacetic acid, by 3,368,97 8 2/ 1968 Irani 252-137 ght of said bar. 3,380,924 4/ 1968 Werdelmann et a1. 252-417 s gfif gf LEON D. ROSDAL, Primary Examiner 214,454 10/1965 Blaser et a1. d 260-502.4 XR 5 ALBRECHT Asslstant Exammer 224,976 12/1965 Farrar et a! 252-117 XR US. Cl. X.R.

226,330 12/1965 Anstett 252'117 252108, 132

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3 511,783 Dated May 12 1970 John Walter Waring It is certified that error appears in the aboveidentified patent and that said Letters Patent are hereby corrected as shown below:

Column 1, line 54 change "in" to --In-.

Column 2, line 25 change "affect" to -effect-- Column 3, line 21 change "manufacture" to -manufactured- Column 5, Table II, subtitle "l p.p.m. Copper/l0 p.p.m. for heading "Percent EHDP" change "9.5" to -O.5.

Column 5, Table III in heading "1 p.p.m. Copper/l0 p.p.m. Iron Added" change "Acded" to Added.

Column 6, Example III, line 67 change "fattey" to --fatty Column 9 Table X, subtitle "l p.p.m. Copper/l0 p.p.m. Iron Added" delete from the figure "22.1" in Column 1.

Column 10, Table XIV, subtitle "No Copper/Iron Added" under heading "Percent EDTA (as free acid) change "0.01" to --0. 02.

SIGNE'II AND SEALED insm (SEAL) EdwardM-FletchwJ m I. BGH'UYIE Amng officer commissioner of Patn FORM PC4050 USCOMM-DC 60376 P59 U 5 GOVERNMENT PRINTING OFFICE I959 O3633 

